Barium strontium titanate and non-ferroelectric oxide ceramic composites for use in phased array antennas

Abstract

A ceramic ferroelectric phase shifting device has been demonstrated using Ba_1?xSr_xTiO₃ (BSTO) ceramics. ¹ As part of an effort to optimize the device performance, various composites of BSTO and other nonelectrically active oxide ceramics have been formulated. In general the composites have reduced dielectric constants, ε′, where ε = ε′-iε″ and reduced loss tangents, tan δ, compared to BSTO. The low dielectric constant and low loss tangent reduce the overall impedance mismatch and insertion loss of the device. In addition, the tunability (change in the dielectric constant with applied voltage) is maintained at a relatively high level (15% with an applied electric field of 1.5 V/μm) for dielectric constants of 200. The combination of electronic properties of these materials offer substantially higher operating frequencies, 10 GHz and above. The microstructures including grain size and phase analysis have been examined using SEM and EDX. X-ray diffraction has been used to identify the presence of any secondary phases formed in the composites. The analysis of the phase formation and compositional variations will be related to the electronic properties of the materials.     

Fabrication of amorphous bulk and multi-phase ceramics by melting method in the HfO2-Al2O3-Gd2O3-Eu2O3system

Ceramics have generally been fabricated from powders by shape forming & sintering methods except for glasses and glass ceramics. Glasses and glass ceramics can be fabricated by melting methods. The melting method has not only higher productivity but also higher shape forming ability than powder processes via forming & sintering methods. Thus we have reinvestigated melting methods in binary and ternary oxides systems to fabricate amorphous bulk ceramics and bulk nano composites. We have successfully fabricated amorphous phases by simple melt solidification methods in ternary eutectic melts in the HfO₂-Al₂O₃-Gd₂O₃system. The present study demonstrates the formation of the amorphous phases in quaternary systems HfO₂-Al₂O₃-Gd₂O₃-Eu₂O₃. Furthermore, we have also succeeded to fabricate nano-structured bulk ceramics, which consisted of constituent oxide grains with 20–100 nm in size, by post annealing of the amorphous phase.     

Co-Modification of Ba5NdTi3Ta7O30 Dielectric Ceramics by Substitution and Introducing Secondary Phase

Co-modification of Ba₅NdTi₃Ta₇O₃₀ dielectrics ceramics was investigated through Pb substitution for Ba and introducing Bi₄Ti₃O₁₂ secondary phase. The dielectric constant increased from 150 to 283, the temperature coefficient of the dielectric constant decreased from –2500 ppm/°C to –1279 ppm/°C, and the dielectric loss decreased to 0.0007 at 1 MHz. Meanwhile, the bi-phase ceramics were investigated to achieve temperature stable ceramics with high dielectric constant and low dielectric loss. As the composition x varied from 0.4 to 0.7 for (1 – x)(Ba_0.8Pb_0.2)₅NdTi₃Ta₇O₃₀/xBi₄Ti₃O₁₂, the temperature coefficient of the dielectric constant changed from negative to zero to positive.     

Thin films of novel ferroelectric composites

Abstract

Composites of BSTO combined with other non electrically active oxides have demonstrated adjustable electronic properteis which can be tailored for use in various electronic devices.^[1,2] These novel composites of barium strontium titanate (BSTO) and oxide III compounds have already exhibited promising results in their ceramic form.^[3] The additive oxides modify the dielectric constant, tunability (change in the dielectric constant with applied voltage), and dielectric loss of the material. One application has been for use in phased array antennas and insertion has been accomplished into several working antenna systems.^[4] To further accommodate the frequencies required by these phased array antennas, thin films of the composites have been fabricated. Preliminary studies have indicated that thin films of such composites exhibit similar behavior as their bulk ceramic counterparts.^[5] The purpose of this study is to investigate the properties of the BSTO/oxide III based compounds in thin film form.     

CHARACTERIZATION OF FERROELECTRIC FILMS UP TO 60 Ghz: APPLICATION TO PHASE SHIFTERS

ABSTRACT

Paraelectric Ba_0.5Sr_0.5TiO₃ films 0.3 μm thick have been deposited by sol-gel on c-axis sapphire substrates. They have been investigated from 1 kHz to 60 GHz using coplanar waveguide transmission lines and interdigitated capacitors. The dielectric constant ε_r is around 300 and the loss tangent is 0.16 at 50 GHz. The tunability is constant with frequency with a mean value of 42%. Analog phase shifters were subsequently fabricated. A 180° phase shift was obtained at 60 GHz with a 17 V bias. The maximum value of phase shift per decibel of insertion losses (at 0 V) is 13°/dB at 30 GHz with a bias of 30 V.     

Dielectric relaxation phenomenon of rare earth Nd3+ modified bismuth layer ferroelectric ceramics fabricated by plasma active sintering method

Abstract

The crystalline structure, dielectric relaxation and ferroelectric properties of the solid solution, Nd _x Bi_4-x Ti₃O₁₂ (NBIT) compound were measured. The Curie temperature of the NBIT ceramics was determined to be 490°C from dielectric measurements. The dielectric constant of the NBIT ceramics shows a small anisotropic property. Polarization switching was observed using a Sawyer-Tower circuit at 50 Hz. Remnant polarizations and coercive fields could not be confirmed since the hysteresis loops were not saturated. The large dielectric relaxation is observed in the frequency range between 100 kHz and 1 MHz.     

Dielectric properties of ZnNb2 O 6 -TiO 2 mixture thin films

ZnNb₂O₆-TiO₂ mixture thin films with multilayer structures were fabricated via a sol-gel spin coating process. TiO₂ layers were deposited on the pre-crystallized ZnNb₂O₆ layers in order to suppress the formation of the ixiolite phase which always forms in the bulk system. The phase constitution of the thin films, confirmed by X-ray diffraction (XRD), could be controlled by the annealing temperatures, which, in turn, influenced the dielectric properties of the thin films. TiO₂ layers crystallized as the anatase phase and then transformed to the rutile phase at temperatures higher than 725^∘C. Dielectric constants of the mixture thin films, measured at 1 MHz with an MIM (metal-insulator-metal) structure, increased from 27 to 41 with dielectric losses below 0.005 as the annealing temperature increased from 700^∘C to 900^∘C. The increase in the dielectric constants was understood to originate from the increasing amounts of the rutile phase. Temperature coefficients of capacitance (TCC) were also measured between 25^∘C and 125^∘C, which showed a decreasing manner from positive values to negative values with increasing annealing temperatures. When annealed at 850^∘C, the TCC of the thin films could be tuned to be approximately 0 ppm/^oC with dielectric constant and dielectric loss of 36 and 0.002, respectively.     

Microwave Dielectric Characteristics of MgTiO<Subscript>3</Subscript>/CaTiO<Subscript>3</Subscript> Layered Ceramics

MgTiO₃/CaTiO₃ layered ceramics with differently stacking were fabricated and the microwave dielectric properties were evaluated with TE₀₁₁ mode. With increasing CaTiO₃ thickness fraction, the resonant frequency decreased and the dielectric constant increased with a near-linear relation for the bi-layer ceramics, while the values of the tri-layer MgTiO₃/CaTiO₃/MgTiO₃ ceramics with thickness ratio of 1:1:1 derived much from the curves of the bi-layer ceramics. The finite element method was used to give an explanation for the differences between the bi-layer and tri-layer ceramics.     

THE ELECTRICAL AND STRUCTURAL PROPERTIES OF Li2CO3 DOPED 0.7(Ba,Sr)TiO3-0.3MgO CERAMICS

ABSTRACT

We have studied the formation and characterization of Li₂CO₃ doped 0.7(Ba,Sr)TiO₃-0.3MgO ceramics for the low temperature sintering and microwave applications. In this study 1 ～ 5 wt% of Li₂CO₃ was added to the 0.7(Ba,Sr)TiO₃-0.3MgO ceramic materials to reduce the sintering temperature. The MgO contents, which added in this experiment, play a role of improving dielectric permittivity such as low frequency dispersion and low loss tangent.

In this paper, we will discuss the crystalline properties, dielectric properties, and the microstructures of Li₂CO₃ doped 0.7(Ba,Sr)TiO₃- 0.3MgO ceramics. No pyro phase was observed in the X-ray diffraction method. Very weak frequency dispersion of dielectric permittivity was observed from the 1 kHz to 1 MHz range. Different grain sizes of Li₂CO₃ doped 0.7(Ba_0.5Sr_0.5)TiO₃-0.3MgO ceramics were observed through the SEM methods.     

Crystallization of Zr Based Oxide with Glass Forming Additives for Gate Dielectric Applications

In this study, Si, Al, and Bi have been investigated as a glass forming additive. Addition of glass forming materials is effective on stabilization of amorphous phase for Zr based films. The higher crystallization temperature results from the more additives. Addition of heavier atom is more effective on enhancing dielectric constant but results in lowering crystallization temperature. Addition of Si results in the most stable amorphous with significant reduction of dielectric constant. When the atomic ratio of Si over (Si + Zr) of about 0.55 is annealed at 950°C for 1 min, any crystallization behaviors are not noticed with dielectric constant of 12. On the other hand, addition of Al causes moderate improvement of crystallization behavior with small sacrifice of dielectric constant. The amorphous films of Zr_{1 ? x} Al _x O _y (X = 0.55) remain amorphous up to 800°C anneals with dielectric constant of 15.     

Microwave dielectric properties of B2O3-added Li2MgTiO4 ceramics for LTCC applications

Li₂MgTiO₄ (LMT) ceramics which are synthesized using a conventional solid-state reaction route. The LMT ceramic sintered at 1250°C for 4 h had good microwave dielectric properties. However, this sintering temperature is too high to meet the requirement of low-temperature co-fired ceramics (LTCC). In this study, the effects of B₂O₃ additives and sintering temperature on the microstructure and microwave dielectric properties of LMT ceramics were investigated. The B₂O₃ additive forms a liquid phase during sintering, which decreases the sintering temperature from 1250°C to 925°C. The LMT ceramic with 8 wt% B₂O₃ sintered at 925°C for 4 h was found to exhibit optimum microwave dielectric properties: dielectric constant 15.16, quality factor 64,164 GHz, and temperature coefficient of resonant frequency -28.07 ppm/°C. Moreover, co-firing of the LMT ceramic with 8 wt% B₂O₃ and 20 wt% Ag powder demonstrated good chemical compatibility. Therefore, the LMT ceramics with 8 wt% B₂O₃ sintered at 925°C for 4 h is suitable for LTCC applications.     

Simultaneous preparation and densification of lead magnesium niobate-based ferroelectrics

Abstract

Ferroelectric lead titanate-doped lead magnesium niobate ceramics have been prepared and densified simultaneously by a new reaction sintering process. At low temperatures, the pyrochlore phase is firstly formed, which induces the expansion of the specimens. When the perovskite phase begins to produce at elevated temperatures, the specimens rapidly shrink, indicating the occurrence of reaction sintering. After sintering at 850°C, monophasic Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ solid solutions with high density are obtained. With an increase in the doping amount of PbTiO₃, the maximum dielectric permittivity and the Curie temperature increase; however, the relaxor characteristics of Pb(Mg_1/3Nb_2/3)O₃ become weakened. With the addition of 15 mol% PbTiO₃, the maximum dielectric permittivity is over 25000 at 1 kHz. It is concluded that monophasic and densified Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ with high dielectric permittivity are successfully prepared by the newly developed reaction sintering process.     

Structure,Ferroelectric, Dielectric and Energy Storage Studies of Ba0.70Ca0.30TiO3, Ba(Zr0.20Ti0.80)O3 Ceramic Capacitors

Ba_0.70Ca_0.30TiO₃-(BCT),Ba(Zr_0.2Ti_0.8)O₃-(BZT) ceramics were fabricated by conventional mixed oxide route to develop inorganic dielectric materials suitable for use as an insulator with high dielectric constant and low energy loss for capacitor applications. The structural phase transition, ferroelectric, dielectric and energy storage properties of BCT, BZT ceramic capacitors were investigated. Room temperature X-ray diffraction (XRD) patterns revealed prominent peaks corresponding to tetragonal perovskite crystal structure for both BCT, BZT solid solutions. Slim ferroelectric hysteresis (P-E) loops were observed for BCT, BZT solid solutions. Temperature dependent dielectric property measurements of BCT, BZT solid solutions have shown a high dielectric constant and low dielectric loss. Room temperature (300K) breakdown field strength and energy densities were obtained from the integral area of P-E loops. For the BCT ceramics, the largest recoverable energy (unreleased energy) density is 1.41 J/cm³ with dielectric breakdown strength as high as 150 kV/cm. For the BZT ceramics, the largest recoverable energy (unreleased energy) density is 0.71 J/cm³ with dielectric breakdown strength as high as 150 kV/cm. Bulk BCT, BZT ceramics have shown interesting energy densities; these might be the strong candidate materials for capacitor applications.     

Dielectric Properties of Bi4−x La x Ti3O12 (0 ≤ x ≤ 2) Ceramics

The dielectric properties of the Bi_4–x La _x Ti₃O₁₂ (0 x 2) ceramics were characterized and discussed together with the P-E relation (polarization vs. electric field). With increasing x, the P-E relation changed from normal ferroelectric hysteresis loops to pure linear relation, which indicated that La³⁺ substitution for Bi³⁺ in Bi₄Ti₃O₁₂ induced a phase transition from ferroelectric to paraelectric state at ambient temperature. Low loss dielectric ceramics with temperature stable dielectric constant were obtained for x > 1.2 in Bi_4–x La _x Ti₃O₁₂ at 1 MHz. And the loss increased in all the compositions when the ceramics were measured at microwave frequencies.     

Thin film BaxSr1-xTiO3 ku- and k-band phase shifters grown on MgO substrates

Abstract

We report measurements of gold circuits fabricated on four Ba_xSr_1-xTiO₃ ferroelectric films doped with 1% Mn grown on MgO substrates by laser ablation. Low frequency (1 MHz) measurements of σ_T and tanδ on interdigital capacitors are compared with high frequency measurements of phase shift and insertion loss on coupled microstrip phase shifters patterned onto the same films. The variation in temperature of both high and low frequency device parameters is compared. Annealed with amorphous buffer layer and unannealed films are compared. Room temperature figures of merit of phase shift per insertion loss of up to 58.4°/dB at 18 GHz and 400 V dc bias were measured.     

Structure and dielectric properties of Cu and (K,Na) doped SrBi2Nb2O9 ferroelectric ceramics

Ferroelectric ceramics, SrBi₂Nb₂O₉ (SBN), Sr_0.8Cu_0.2Bi₂Nb₂O₉ (SCBN) and Sr_0.8K_0.1Na_0.1Bi₂Nb₂O₉ (SKNBN) were prepared by a solid state reaction process. X-ray diffraction analysis shows that the alkali and Cu almost diffuse into the SBN lattice to form a solid solution during sintering and some slight secondary phases was detected. The effect of alkali and Cu on dielectric properties of the SBN ceramics was discussed. The dielectric loss factor of (K,Na) doped SBN ceramics degraded considerably to 0.01 and their frequency and temperature stabilities were enhanced. The dielectric constant was enhanced by approximately 60% and the Curie temperature (Tc) was also improved for Cu doped SrBi₂Nb₂O₉ ceramics.     

Low-temperature sintering and electrical properties of (1−x)Pb(Zr0.5Ti0.5)O3-xPb(Cu0.33Nb0.67)O3 ceramics

Electrical properties and sintering behaviors of (1 − x)Pb(Zr_0.5Ti_0.5)O₃-xPb(Cu_0.33Nb_0.67)O₃ ((1 − x)PZT-xPCN, 0.04 ≤ x ≤ 0.32) ceramics were investigated as a function of PCN content and sintering temperature. For the specimens sintered at 1050^∘C for 2 h, a single phase of perovskite structure was obtained up to x = 0.16, and the pyrochlore phase, Pb₂Nb₂O₇ was detected for further substitution. The dielectric constant (ε _r), electromechanical coupling factor (K_p) and the piezoelectric coefficient (d ₃₃) increased up to x = 0.08 and then decreased. These results were due to the coexistence of tetragonal and rhombohedral phases in the composition of x = 0.08. With an increasing of PCN content, Curie temperature (T_c) decreased and the dielectric loss (tanδ) increased. Typically, ε_r of 1636, K_p of 64% and d₃₃ of 473pC/N were obtained for the 0.92PZT-0.08PCN ceramics sintered at 950^∘C for 2 h.     

High dielectric constant in (1 − x)SrTiO3/xCuO composite ceramics

Semiconductive secondary phase CuO was introduced into SrTiO₃ ceramic matrix to yield dielectric composite ceramics with high dielectric constant. The dense composite ceramics could be obtained by sintering at 1050°C in air for 3 h, in which the co-presence of SrTiO₃ and CuO/Cu₂O was confirmed. The dielectric constant of the present composite ceramics increased firstly and then decreased with increasing the content of CuO, and the highest dielectric constant was obtained at x?=?0.4. There were steps and peaks on the curves of dielectric constant vs temperature and dielectric loss vs temperature, respectively, and the peak temperatures of dielectric loss indicated the Debye-type relaxation.     

Dielectric tunability and microwave properties of Ba0.5Sr0.5TiO3-BaMg6Ti6O19 composite ceramics for tunable microwave device applications

Ba_0.5Sr_0.5TiO₃-BaMg₆Ti₆O₁₉ microwave composite ceramics with low dielectric constant and relatively high tunability were fabricated via the solid-state reaction method. The microstructures and microwave dielectric properties of the composite ceramics have been investigated. BaMg₆Ti₆O₁₉ and Ba_0.5Sr_0.5TiO₃ can be friendly coexistent in the composite material system without obvious chemical reactions. With increasing content of BaMg₆Ti₆O₁₉ from 10 wt.% to 60 wt.%, the dielectric anomalous peaks of ferroelectric-paraelectric phase transition for the composite ceramics are suppressed and broadened. The dielectric constant can be effectively tailored from 2035 to 129. For composite ceramics with 60 wt.% content of BaMg₆Ti₆O₁₉, the dielectric loss still keeps around 0.002 and the tunability is 13.4% measured at a dc-applied electric field of 30 kV/cm. The Q value of composite ceramics with 20 wt.% content BaMg₆Ti₆O₁₉ is 367 and the dielectric constant is cut down to 665 at the microwave band of 1.579 GHz.     

Strain tensor effects on SrTiO3 incipient ferroelectric phase transition

Structural distortion of ferroelectric thin films caused by film strain has a strong impact on the microwave dielectric properties. SrTiO₃ thin films epitaxially grown on (110) DyScO₃ substrates using molecular beam epitaxy (MBE) are extremely strained (i.e., ～1% in-plane tensional strain) from 3.905 Å of bulk SrTiO₃. The room temperature dielectric constant and its tuning of the films are observed to be 6000 and 75% with an electric field of 1 V/μm, respectively. The control of strain in SrTiO₃ provides a basis for room temperature tunable microwave applications by elevating its phase transition peak to room temperature. Also, a significant in-plane anisotropy in dielectric constant and tuning was observed in these SrTiO₃ films. The observed in-plane anisotropic dielectric properties have been interpreted based on the phenomenological thermodynamics of film strain.